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The ability of an atmospheric aerosol to take up water or to participate in heterogeneous reactions is highly influenced by its phase state – solid, semi-solid, or liquid. These changes in phase state can be predicted by glass transition temperature (Tg), as particles at temperatures below their Tg will show solid properties, while increasing the temperature above their Tg will allow for semi-solid and eventually liquid properties. Historically, measurements of the Tg of bulk materials have been studied in order to model the phase states of aerosols in the atmosphere; however, these methods only permit an estimation of aerosol Tg based on their bulk chemical composition. Determining the Tg of individual particles will allow for more accurate model predictions of aerosol phase state. Herein, we apply a recently developed method utilizing a nano-thermal analysis (nanoTA) module coupled to an atomic force microscope (AFM), to determine the Tg of individual secondary organic aerosol (SOA) particles generated from the reactive uptake of isoprene epoxydiol (IEPOX) onto acidic ammonium sulfate aerosol particles. NanoTA works by using a specialized AFM probe which can be heated while in contact with a particle of interest. As the temperature increases, the probe deflection will first increase due to thermal expansion of the particle followed by a decrease at its melting temperature (Tm). The Tg of the particle can then be determined from Tm using the Boyer–Beaman rule. We compared the Tg of IEPOX-derived SOA particles generated at relative humidity (RH) of 30, 65, and 80%, and found that increasing RH from 30 to 80% led to a decrease in average Tg of 22 K, indicating less viscous particles at higher RH conditions. Our measurements with this technique will allow for more accurate representations of the phase state of aerosols in the atmosphere.
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Atomic Force Microscopy: An Emerging Tool in Measuring the Phase State and Surface Tension of Individual Aerosol Particles
Atmospheric aerosols are suspended particulate matter of varying composition, size, and mixing state. Challenges remain in understanding the impact of aerosols on the climate, atmosphere, and human health. The effect of aerosols depends on their physicochemical properties, such as their hygroscopicity, phase state, and surface tension. These properties are dynamic with respect to the highly variable relative humidity and temperature of the atmosphere. Thus, experimental approaches that permit the measurement of these dynamic properties are required. Such measurements also need to be performed on individual, submicrometer-, and supermicrometer-sized aerosol particles, as individual atmospheric particles from the same source can exhibit great variability in their form and function. In this context, this review focuses on the recent emergence of atomic force microscopy as an experimental tool in physical, analytical, and atmospheric chemistry that enables such measurements. Remaining challenges are noted and suggestions for future studies are offered.
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- Award ID(s):
- 1801971
- PAR ID:
- 10232170
- Date Published:
- Journal Name:
- Annual Review of Physical Chemistry
- Volume:
- 72
- Issue:
- 1
- ISSN:
- 0066-426X
- Page Range / eLocation ID:
- 235 to 252
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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The ability of an atmospheric aerosol to take up water or to participate in heterogeneous reactions is highly influenced by its phase state – solid, semi-solid, or liquid. These changes in phase state can be predicted by glass transition temperature (Tg), as particles at temperatures below their Tg will show solid properties, while increasing the temperature above their Tg will allow for semi-solid and eventually liquid properties. Historically, measurements of the Tg of bulk materials have been studied in order to model the phase states of aerosols in the atmosphere; however, these methods only permit an estimation of aerosol Tg based on their bulk chemical composition. Determining the Tg of individual particles will allow for more accurate model predictions of aerosol phase state. Herein, we apply a recently developed method utilizing a nano-thermal analysis (nanoTA) module coupled to an atomic force microscope (AFM), to determine the Tg of individual secondary organic aerosol (SOA) particles generated from the reactive uptake of isoprene epoxydiol (IEPOX) onto acidic ammonium sulfate aerosol particles. NanoTA works by using a specialized AFM probe which can be heated while in contact with a particle of interest. As the temperature increases, the probe deflection will first increase due to thermal expansion of the particle followed by a decrease at its melting temperature (Tm). The Tg of the particle can then be determined from Tm using the Boyer–Beaman rule. We compared the Tg of IEPOX-derived SOA particles generated at relative humidity (RH) of 30, 65, and 80%, and found that increasing RH from 30 to 80% led to a decrease in average Tg of 22 K, indicating less viscous particles at higher RH conditions. Our measurements with this technique will allow for more accurate representations of the phase state of aerosols in the atmosphere.more » « less
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Abstract Atmospheric aerosols are complex mixtures of different chemical species, and individual particles exist in many different shapes and morphologies. Together, these characteristics contribute to the aerosol mixing state. This review provides an overview of measurement techniques to probe aerosol mixing state, discusses how aerosol mixing state is represented in atmospheric models at different scales, and synthesizes our knowledge of aerosol mixing state's impact on climate‐relevant properties, such as cloud condensation and ice nucleating particle concentrations, and aerosol optical properties. We present these findings within a framework that defines aerosol mixing state along with appropriate mixing state metrics to quantify it. Future research directions are identified, with a focus on the need for integrating mixing state measurements and modeling.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1146/annurev-physchem-090419-110133
